Process of conducting chemical reactions



Nov- 4, 19 7- J. J. ALLINSON PROCESS OF CONDUCTING CHEMICAL REACTIONS 2Sheets-Sheetl Original Fil'ed Nov. 27, 1942 1 a. r? 0x17442- CMLM Flu/0NW4 947- J. J. ALLINSON PROCESS OF CONDUCTING CHEMICAL REACTIONSOriginal Filed Nov. 2'7, 1942 2 Sheets-Sheet 2 a -a at, 19.7 2,429,980

mooass or CONDUCTING aaac'nons John J. Ailinaon, El Dorado, Aria,asslgnor to LionOil Company, a corporation of Delaware Originalapplication November 27, 1942, Serial No. 467,108. Divided and thisapplication May CHEMICAL 6, 1944, Serial No. 534,439 7 12 Claims. (01.196-52) I 1 This invention pertains to an apparatus and process ofconducting chemical reactions. It relates in particular to the type ofreactions which can be promoted in the vapor phase, especially catalyticreactions.

One of the objects of this invention is to provide means whereby gaseousfluids and vapors can be caused to react catalytically employing aloosely packed catalyst mass of predetermined thickness with means forcontrolling the temperature of fluid supplied to and removed from thecatalyst bed. l

Another object is to provide ready means for heating or cooling areacting fluid intermediate its travel through a catalyst mass.

Another object is to introduce one of a plurality of reactants into afluid stream in which reaction occurs, in stages in the passage of thestream throughthe mass of catalyst, meanwhile controlling thetemperature of the stream.

Other objects are evidenced by the disclosures of this specification.

The invention comprises passing a reactant fluid as a streamsubstantially horizontally through a confined, supported column ofloosely packed particles or pieces of catalyst material, the catalystmass being of predetermined thickness and adapted to downward movementunder control, and then immediately contacting the fluid with atemperature controlled surface. The process reactions include oxidation,reduction, hydration, dehydration, absorption, chlorination, cracking,polymerization, depolymerization, and certain other vapor phasereactions. The process also includes the treatment of solids such as thedryin of granular materials, sand, catalytic materials and the like.

One form of apparatus for practicing my invention is shown in elevationin Figure 1, a portion of the outer casing being cut away to show theinterior in section.

Figure 2 depicts one form of inner bailie unit; half of the unit isshown in section and half of it in elevation.

Figure 3 is a top view of the bafiie shown in Figure 2.

Figure 4 shows in elevation one of the outer bafiles of the outer seriesof baflles with one means of support.

Figure 5 is a top view of the outer baiile shown in Figure 4.

The same system of lettering is used-through-I out the figures. However,in Figures 4 and 5, the number 5|, not shown in the other figures,designates one means of supporting the outer baffles; the member 5|hooking onto lugs 60 pro-- vided for the purpose adjacent wall 9- ofFigure 1. In Figure 1, the catalyst confining chamber I is supplied withcatalyst from reservoir 2 through valvev 3; catalyst is shown at 4. Thetubular member 20 located in the middle of the catalyst bed extendingfrom top to bottom has ports 8 favorably located for the passage of afluid into the catalyst mass, and a series of baflie plates 6substantially conical and so favorably located with respect to a secondseries of bailles I as to co-act with them in confining the catalyst inthe reaction zone substantially as an annular column;

' said bailles I are each shaped much like the frustum of a cone. Fluidsfor contacting the catalyst mass are passed into tube 20 from beloweither through valves ll, l8, and I9 and 48 or from above through valvesi'|--A, i8-A and l9A, 48A and 50, and in either case they enter thecatalyst mass through ports 8 and from beneath baflles 6, traversing thecatalyst mass in substantially a horizontal path and substantiallyradially outwardly, passing into the space adjacent the outer bafliesand into contact with the temperature controlled wall 9 which co-actswith wall In in confining a temperature-control fluid 36; the wholeouter jacket is designated II. baflles I2, lZ-A, l3 and I4 support thecatalyst mass to a large extent maintaining it in a freeflowingcondition whereby arms such as those shown at l5 scrape it off of therotating table l6 at a rate varying under control with the speed ofrotation of said table and with the length of said arms, Means ofdischarging the catalyst or other contact material into receiver 51 isshown at 2! with control valve 22. Fluids entering reaction chamber Ifrom' below through I! and I9 are caused to mix in mixing chamber 24;this chamber is not shown above but can readily be provided when its useis indicated. Valve ,50' controls a supply of cooling fluid which may bewater mist or other medium. Means for rotating table l6 are indicated bygears 52 and 53,,

shaft 54, connected with speed-control gear-box 55 which is beltconnected to motor 56 which is are promoted in the mass of solids, underwhichconnected to a suitable source of power.- Fluid 3B circulatesthrough jacket ll which jacket becomes a boiler when high temperaturereactions condition the heat of reaction is utilized and proper boilerconnections are made as diagrammatically indicated by tank 3| havinginlet 32 for cooling fluid which is supplied to the jacket through 45for regulating the supply'of a cooling fluid Special which may be steam,water mist or other medium. Thermocouple wells 25 and 26 are providedfor thermocouples used in recording temperature of the mass 4; noconnec'tions'are shown because standard practice is employed. Ballie I2Ais complementary to baffle l2 and is used along with l2 when thecatalyst mass is very dense and heavy; when used alone ithas the effectof allowing the catalyst adjacent the outer baflles 'l to flowdownwardly at a faster rate than it flows adjacent the inner series ofbaflles 6, contrariwise, when l2-A is omitted and I2 is used alone thecatalyst adjacent the inner series\of baiiles 6 flows downwardly at thefaster rate, provided in each case the baiiles l2 and I 2---A extend farenough into the mass of catalyst and their angles of slope downwardlyare not too steep. Although any chosen fluid may be admitted to 20 andinto mass 4, for the purpose of clearly describing my invention themajor valves, and the fluids they control, are respectively as follows:I1, 41 and l'l-A are for air; l9 and l9-A, combustible aeriform fluid;l8, l8-A and 43 are for steam, superheated or saturated; 48 and 48- -Aare for hot gases; and 45 is for any suitable aeriform cooling fluid andmay be air or steam.

Before describing detailed operation of the process with specificreference to a particular chemical reaction, I prefer to call attentionto a number of reactions which can effectively be carried out in thedescribed apparatus, with brief general reference to procedure.

The drying of granular solids or solids in a state of small division isa simple application of the invention; the solids may be coal, carbon, acatalyst, or other material typified here, for example, as sand, asfollows:

Example I.-Re,ferring to Figure 1 Introduce the moist sand into chamber2 through the top charging door leaving valve 3 open. The sand will soonfill chamber l substantially as shown ,in Figure 1. Hot gases are nowpassed through 48A and "into the mass of sand 4 through ports 8, therebywarming the sand, vaporizing water therefrom into the gas stream whichstream is removed adjacent baiiles 1 as shown by the arrows and passedthrough outlet 40 and valve 4|. Table I6 is rotated and a rate ofrotation is adjusted'to co-act with the rate of supply of hot gaswhereby the sand is dried but not discharged too hot through 2| and 22.If the sand is too hot the rate of rotation of table I6 is increased byadjusting speed control gears in box 55, or the rate of supply of hotgas is decreased by throttling valve 48-A, or cooler gas is suppliedthrough 48-A, or combinations of, these procedures arepracticed; thetemperature of the gases passing through 40 should not be below the dewpoint of water. Reservoir 2 is kept reasonably full of sand throughoutthe operation. In this example it is not necessary to circulate coolingfluid through jacket ll. When it is desirable to discharge the sand hotthe hot gases supplied to I should be admitted through 48 instead ofthrough valve 48A. This general procedure is applicable to therevivification of catalysts, gas treatment of catalysts, drying of orefrom mineral washing tables, drying coal and other crushed products. Thefluid used of course is varied to suit the material treated and objectsought. In the simple treatment of sand one can use combustible gas andair, burning the gas, in effect, in contact with the sand, or anotherheating fluid may be used, whereas with crushed coal, prepared forcoking, air usually should not be used alone, rather superheated steam,with or without combustion products, is preferred, thus avoidingoxidation of the coal, preserving its coking qualities. Incidently coaltreated in thismanner is coked in a carbonizer in half the time normallyrequired. The most economical effect is obtained with good coking coalby burning premixed gasand air in or substantially along with steam andpassing the mixture of the three through the coal bed at a temperaturebelow its plastic temperature. This is accomplished by controllingvalves l1, l9, and N3, the upper reactant-fluid valves being closed. anddischarge valve 4| open. With minerals comprising sulphides it isusually preferred to burn a gas-in contact with the crushed mineralmatter using excess air thereby promoting the combustion of saidsulphides to oxides, sulphur dioxide also being formed. The treatment ofcatalysts commonly requires that a definite atmosphere be used such ashydrogen, air, etc. With refractory materials, commonly it is requiredthat carbon be burned off of their surfaces, in which case air alone issupplied as through valve I! or hot gas through 48 and air through [1.

Controlled combustion and partial or incomplete combustion reactions inwhich the solid mass is itself a reactant, may include the carbonizationof wood with the production of char, carbonization of lignite,sub-bituminous coal and other materials which are carbonizable and whichwill flow at elevated temperatures, and they are typified in a generalway v referring to Figure 1 as follows;

Example II.Carbonization of sub-bituminous coal As in Example I, chamberI is filled with crushed and rather uniformly sized pieces of the coal.A hot fluid, for example superheated steam is introduced into 20 byopening valve l8A, causing hot steam to pass through the mass .4 ofcoal. In this case table I6 is not rotated until the temperature of thegases and water vapor leaving the reaction chamber I through 40 is aboveC. This treatment is continued and after the carbonaceous mass is fairlywell heated'table I6 is rotated at a rate adapted to obtain the desireddegree of carbonization of the coal. A slow rate of rotation yields anover-carbonized char whereas a high rate yields an under-carbonizedchar; an analysis of the char will show the de- 55' gree ofcarbonization. After the operation is under way hot gaseous products ofcombustion can be substituted at least in-part for the superheated steamby opening valve 48A, with or without some air which may beintroduced-through |lA. When the recovery of particular by-products ofdistillation in the offtake vapors is desired the amount of air used'iscarefully controlled or eliminated. However, the use of air, as throughl'l-A with or without added combustible gas through l9-A, promotingcombustion within said mass, decreases carbonizin time and decreases theamount of steam used per ton of solid combustible carbonized. When airis used as described, the temperature in the mass of, fuel in process ishighest at the level of the lower baflles of series 6 and 1, and coolingis desired at a point close to these baflies; under these conditionscooling fluid, steam or water mist is admitted through acaaoso cientlyhigh in this example to prevent appreciable condensation and settlingout of distillation products against surface 0 of said jacket:

this is accomplished by limiting the amount of circulation of said fluid36 and by the selection of said fluid. Water can be used in general, andtemperatures above 100 C. attained when the water is confined underpressure. with high temperature gases the jacket aflords a means ofsuperheating the process steam. Other highboiling liquids may be usedinplace of water as fluid 36.

Example III .Distillation of sawdust When sawdust is distilledsubstantially as outlined in Example 11, using superheated steam,turpentine spirits and other products of distillation are obtained. Itis found that after the distillation is fairly well started there is astrong exothermic reaction which alone is sufllcient to carbonize thesawdust. Accordingly very little steam is required for the late stage ofcarbonization, except for flushing purposes, and the rate of traveldownward chiefly depends on the rate of initiating the exothermicreactions; in other words, it is more'essential that the superheatedsteam pass through the bed of sawdust adjacent the upper co-actingbaflles Ii and I of Figure 1 than through the mass at lower levels. Thismay be accomplished in two ways, or a combination of both, namely thenumber and size of the ports 8 adjacent the lower co-acting baillescanbe and are smaller than the upper level ports; fewer ports may beemployed or they can be limited at the lower levels. I prefer to usesmall ports at the latter levels rather than none or the useofblocked-off sections containing the lower ports. The sawdust can becompletely carbonized or incompletely carbonized according to the heatenergy applied to it as steam, as combustion gases, as air forcombustion, and according to the rate of flow of sawdust as determinedby the speed of rotation of table [6 and according to the amount ofcooling fluids admitted to the lower portionof the reaction chamberthrough 42 and-44. Example IV.-Reviviflcation of a solid catalystReferring to Figure 1 and considering the catalyst to be black copperoxide which exists in more or less granular condition and which ispartly reduced, the catalyst is charged into chamber I from reservoir 2until it is filled substantially as shown in the figure. Warm air isintroduced throughl'lA and 20, passed through ports 8, through thecatalyst mass 4, out adjacent the outer baffles I, through oiltake 40and valve 4|. The oxidation of the reduced copper occurs at relativelylow temperatures, the reaction is represented by Equation 1 as follows:

(1) 2Cu+O2=2CllO The reaction is exothermic and heat is generated to theextent of 34.9 kg. calories per gram formula weight or per 79.57 gms. ofCuO equivalent to 986 B. t. u. per pound of copper oxidized. Because ofthe heat of reaction it is only necessary to initiate oxidation by usingwarmed air after which air at about room temperatures can be used; thetumbling action and mixing of the particles of catalyst are helpful inavoiding overheating and in producing a uniformly revivified catalyst.Table I6 is rotated, after oxidation is started, at a rate which removesthe catalyst substantially as fast as it is revivified, which isdetermined by test. oxidizing 1000 lbs. of copper to copper oxide (CuO)requires theoretically 14,170

6 cubic feet of air; actually the amount of air required is somewhatmore than this even when the initial temperature of the air at the startof processing is 150 to 200 C.

It will-be noted that copper oxide functions as an active catalyst tooxidation and certain other types of reactions at temperatures of theorder to 310 C. and in some cases at temperatures even higher than -310C. The apparatu shown in Figure 1 can be used to carry out the catalyticreactions themselves by introducing the reactant fluid through suitableconnections to conduit 40, through l9A, 20, and on through the catalystmass 4; the oxygen or air for the reaction and for the maintenance ofthe catalyst in active condition is introduced along with the materialto be oxidized, as by opening valve l'l-A, avoiding an appreciableexcess of air over requirements. The reaction products in thi case leavethe catalyst mass in the usual manner 'as described, at substantiallythe temperature of the catalyst mass, the heat of reaction beingutilized to heat fluid in jacket H, which latter, in cooling the streamof reaction products immediately after their formation, prevent sidereactions and extraneous reactions from occurring in the fluid streamafter leaving the catalyst mass. Operating my invention in this mannertable I6 is normally rotated only suflicient to maintain the catalystmass loose and clean and to make room for replacement catalyst.required, is introduced simultaneously with the reactant fluid through50, which fluid may be atomized water, steam, or other material when 50is suitably connected with such a source of supply. Table I6 may berotated at such a speed that fresh, cool catalyst is rapidly supplied tochamber l. Periodically the' catalyst may be steamed and air treated insitu without the pres, ence of other reactants.

Examples of oxidation reactions which may be conducted in this mannerwith a solid oxidation catalyst, such as copper oxide, vanadiumpentoxide, silver, silver oxide, gold, platinum, palladium, and others,are the following:

(A) Oxidation of naphthalene to phthalic anhydride; vanadium pentoxidebeing a good catalyst. This highly exothermic reaction must be conductedin such a manner that the reactants and reaction products are notoverheated, in order to prevent the formation "of considerable tarrymatter. The reaction is indicated by Equation 2.

The heat of reaction is 6310 B. t. u. per pound of solid naphthaleneconverted according to Equation 2. A satisfactory operating temperaturefor promoting the reaction of Equation 2 is about 400 C. The reactionproducts, after condensing and removing the organic components comprise,on the dry gas basis, chiefly nitrogen and carbon dioxide, which aresatisfactory diluents for recirculation with the naphthalene as atemperature controlling medium. By periodically interrupting the flow ofreactants into the catalyst bed and treating the catalyst to revivifyingand temperature control fluids, the operation becomes cyclic, andtemperature more exact without the use of an excess of diluent fluids.

The naphthalene vapor is introduced through 46 and Ill-A and. the airthrough l'l--A, steam may be introduced through |8A and recircu latedgases through 48-A, and the stream of reaction products pass out through40 and 4i.

Cooling fluid, when taneously (B) Formaldehyde is another product ofincomplete oxidation and is made practicing my invention substantiallyin accordnce with Equation 3 My experiments show that in the catalyzedconversion of methanol to formaldehyde it is an economy to use air andsome steam in admixture with the methanol preparatory to catalyticconversion. The mixture is passed through the catalyst mass in themanner described, the catalyst is removed by rotation of table l6,Figure 1, sufficiently to keep the catalyst bed loose and clean; theoperation is conducted at substantially atmospheric pressure and heatgenerated is recovered by absorption in the fluid in jacket ll.

Special means for initiating combustion have not been shown in thefigures because means known in engineering practice will be followed.

velocity of flow through the catalyst mass is maintained at a high rateconsistent with the speed of reaction, and, referring to Figure -1, thecooling wall 9 is preferably kept at a temperature below about 150 C.The gaseous products of combustion besides formaldehyde are chiefly ni-However, in order to make disclosure complete either of severalprocedures maybe followed, namely, (a) blast hot gases through valve48-A until the temperature of the mass of solids 4 adjacent baflles 6 ofFigure 1 is above the ignition temperature of the combustible fiuid tobe burned and then admit said fluid through l9A, the air for combustionthrough i|A, or (b) when filling the reaction chamber with solidsintroduce enough ignited charcoal to fill the annular space between theseries of baflies 6 and l, the rest of the charge being the chosenpreferred contact material; as the mass is blasted with air through terof'prime importance in obtaining the most efiicient results is to socontrol the thickness of the catalyst mass between the inner series ofbaflies 6 and the outer serie I that the reaction products are notcaused to linger too long in contact with the heated catalyst. In thismanner more of the heat of reaction is carried out of the catalyst massas sensible heat of the reaction products. The result is accomplished byproperly proportioning the mean diameters of the two series of bafllesand to some extent regulating linear velocity of flow of reactantsthrough the catalyst bed.

(C) The production of aldehydes by dehydrogenation of monohydricalcohols also comes within the confines of my invention, the reactionbeing typified by Equation 4.

(4) CH3OH=HCHO+H2 and certain combinations including silver with smallamounts of platinum, manganese oxide, and

some partially reduced metal oxides, is catalytic to this process, whichmay be conducted at atmospheric pressure and at temperatures within therange 200 to 350 C. Because of the tendency of the alcohols to formolefins and water when heated in this temperature range, the use of somesuperheated steam in the reactant fiuid stream is helpful with theheated alcohol vapor; this substantially eliminates the dehydrationreaction. It is possible to cause two reactions to occur simulinproducing formaldehyde from methanol, namely the one shown above asEquation 4 and the oxidation reaction shown in Equation 5, which isexothermic.

ll-A the charcoal is consumed and the contact material gradually takesits place and becomes heated, the thermocouple being a guide as to thetemperature when connected with a pyrometer potentiometer, or (c) duct20 can be filled from the top flange with ignited charcoal and airblastin of it will bring the temperature of the solids 4 up to thestarting temperature.

' (D) Absorption of condensable components of gaseous or vaporous fluidsis practiced employing this invention by using as the "catalyst mass anabsorbent or adsorbent, including such materials as active carbornsilicagel, alumina, aluminum oxide gel, clay, other metal oxides, metalsilicates and other solids. In thiscase, referring to Figure 1, table I6is rotated, slowly, rapidly or intermittently according to the need forremoving the adsorbent mass. Not only are lighter hydrocarbons adsorbedfrom such gases as natural gas, refinery gases and the like, whichhydrocarbons include propane, butane, pentane, hexane, some highermolecular weight members of the series, and light unsaturatedhydrocarbons, but it is possible by controlling the temperature of theadsorbent to make preferential separations, For example, treatingnatural gas at ordinary temperatures, 15 C., employing a rather thickbed of carbon as adsorbent, natural gasoline is adsorbed which containssome propane and butanes, whereas at somewhat higher temperaturespropane is not adsorbed and very little butane is adsorbed. Preferentialadsorption of unsaturated hydrocarbons in refinery hydrocarbon fiuids isobtained by controlling the temperatures of the massof adsorbent, thesupply of said fluid, as well as by the choice of the adsorbent used andthe periodic treatment of said adsorbent. Clay and alumina, for example,promote polymerization and adsorb certain sulphur compounds, and poly-.mers. These are largely removable by steaming by controlling thetemperature of the fluid sup plied to-cooling Jacket I I,Figure 1.

Sulphur dioxide and hydrogen sulphide are adsorbable on silica gel andcarbon and they can be caused to react with one another" at a. rapidrate in contact with either of these materials at ratherlow'temperatures, forming sulphur at a temperature below its meltingpoint; the reaction being exothermic it is necessary to employ dilutemixtures of these gasesin a common diluent or rovide a cooling mediumfor absorbing the generated heat, or employ both methods of control.Much of the sulphur is entrained in the gas. The rotation of table I6 ofFigure 1 keeps the catalyst-adsorbent in a loose condition so that thesulphur passes on entrained in the gas in a fine state of sub-division.A cooling fiuidis circulated through the jacket II in this case.

(E) Maleic anhydride is prepared in substantially the same manner asoutlined above for phthalic anhydride, it being an oxidation product ofbenzene, obtained at about 400 C., using vanadium pentoxide catalyst, orother suitable oxidation catalyst, by direct oxidation.

(F) -Foul gas may be treated by passing a mixture of it with air throughthe bed of catalyst which, in this instance, may be fine-size coke,

along with suiiicient air to maintain the coke at a red heat or hotter,burning any combustible matter in the foul gas; the outlet gas, ortreated gas, is then less offensive. Using solid refractory material ascatalyst, such as crushed fire brick, the catalyst is heated in place toa red heat by burning a combustible gas with air in contact therewith inthe manner outlined above, then the foul gas, plus air, i introduced asa steady .mixed stream into the heated catalyst mass with additionalcombustible gas if and as required to maintain the catalyst at a redheat; the sensible heat of the reacted gas stream is utilized asdescribed. Only infrequent replacement of the catalyst is necessary inthis case.

Example V.--C'racking hydrocarbons and referring to Figure 1 In thethermal decomposition of hydrocarbons, such as petroleum fractions, thematter of control of temperature, of time of contact of the reactantmaterial with the catalyst, of'the duration of time reactionproductsremain at elevated temperature and of concentration of diluent fluid areall factors of major importance in obtaining optimum results. formedunder given set of conditions is largely destroyed by further reactionif it is maintained at high temperatures over any appreciable amount oftime. Because this invention is believed to be particularly applicableto reactions conducted under such conditions and because it hasparticular bearing on cracking and re-forming of hydrocarbons, I preferto give complete details of operation employinga. volatilizablepetroleum hydrocarbon as basic raw material in this example. A mixtureof superheated steam and the heated vapors of said hydrocarbon is causedto pass through 20 by opening valves adapted to Butadiene which may besupply these materials such as I8A and I9-A,

silica, metal oxide, or other catalyst adapted to facilitate thecracking of said hydrocarbon. The stream of gas-steam mixture is passedfrom 20 intov the catalyst mass 4 at a velocity suflicient only toprovide the chosen time of contact with introduced said mass, usuallywithin the limits 0.1 second to 4 seconds according to the completenessof reaction sought the velocity is low enough so that the mass ofcatalyst is not carried away in the gas stream. The gas stream withreaction products is then quickly cooled by contact with surface 9 ofjacket II, and is passed out through oiltake 40 for further treatmentand removal of products of reaction. Meanwhile, a fluid 36 is circulatedthrough jacket II for the double purpose of cooling reaction productsand recovering some of the sensible heat of the gas stream. Usingsuperheated steam at 540 C. and heated hydrocarbon in the vapor phase at600 C. in equal volumes, the mean temperatur of the mixture is commonlyless than half the sum of the two temperatures, being, in thisinstance,about 550 C. Although this temperature sufllces for certain crackingreactions, it is lower than optimum temperature for making many desiredend products such as unsaturates, including those with more than onedouble bond; butadiene and isoprene are obtained in optimum amounts athigher temperatures, namely 750 C. to about 850 C., and the time ofexposure of hydrocarbon vapors to these temperatures should be veryshort. Instead of increasing the amount of steam or the degree fsuperheat thereof, it is frequently advantageous and simple of controlto burn a hydrocarbon in air or in another oxidant in close proximity toor in the reaction chamber so that the hot combustion products, withoutexcess of air, are v into the gas-steam mixture in amounts sufiicient toraise the temperature of the whole to 600 to about 900 C. or somewhathigher. Since a short time of exposure to contact with solids at thistemperature is desired, the number of baiiles in series 6 and I is lessthan for longer contact periods, and the relative sizes of the baflles 6andv I are such that a relatively thin mass of solids only is maintainedbetween them. The mass ofcatalyst supported between 6 and I may have amean thickness of 6 inches or less, or more than 2 feet, according tothe contact desired; a thickness of 18 to 20 inches is quitesatisfactory for many cracking reactions. Table I6 is rotated veryslowly or intermittently, suff cient to keep clean active hot catalystinthe region of baflles 6 and I. When cracking or reforming reactants at700 C. or more, some carbon forms when certain high-boiling hydrocarbonsare used as raw material, and this carbon adheres to the catalyst mass4. In order to avoid more complete cracking it is usually desired thatthe catalyst be as free from carbon as possible; therefore, the regularremoval and replacement of catalyst 4 is essential under theseconditions.

During this downward travel of. said catalyst steam is admitted tochamber I through 42' and 43; this not only cools the outgoing catalystbut it also cleans and refreshens it, reacting with carbon, and carriesheat back into the reaction zone. Thus, when using a contact catalystsuch as crushed firebricks, with or without a metal or metal compoundthereon, the particles are commonly in suitable condition to be returnedto charging hopper 2 after discharging from the bottom of I. When thetemperature of the catalyst is somewhat too low for cleaning asdescribed, air is also admitted to chamber I through 4'1, In order toeliminate-the necessity of moving the catalyst downwardly at too rapid arate or too often, I find it sometimes is quite helpful to interrupt theoperation at determined intervals of time and make a steam-air "run"whereby car- 11 bonaceous material is cleaned from the catalyst; thismakes the operation cyclic. The extentto which this can be carried outis limited, with metal catalysts, unless theoperation is followed bytreatment with reducing gases, for reasons which are obvious. Employingmetal catalyst in the form of shot it is a simple matter to obtainsatisfactory results either by the downward contlnuous flowing of thecatalyst or-by interrupted flow of the catalyst accompanied byoccasional treatment with an aeriform fluid in situ.

Hydrocarbon reactions which can very effectively and advantageously becarried out substantially as described arerepresented, in effect, by

Naphtha and gas oils are similarly crackable.

Results indicated by Equations 7, 8, 9 and 10 occur within thetemperature range of 450 to 650 C, substantially without deposition ofcarbon. Copper or nickel catalyze the reactions but copper is preferred.Aromatic compounds are produced as the cracking temperature is increasedabove 700 C., in increasing amounts. Copper let down on or supported oncrushed refractory material such as alumina or firebrlck is an excellentcatalyst for these reactions; copper shot can be used in a definitetemperature range.

Although it is well known that hydrocarbons, heated sufliciently high,will crack, forming products of lower molecular weight, and ultimatelyforming hydrogen and carbon, so far as I am aware, it has not been shownthat when a stream of hot hydrocarbon vapor mixed with superheated steamand air or other combustion supporting fluid is passed to a bed of hotcatalyst at a velocity greater than the speed of flame propagationthrough the mixture, and then passed through a layer of catalyst at alow enough velocity for combustion of a portion of the combustiblematter of the mixture to occur within or adjacent the catalyst,releasing sufficient heat to maintain the catalyst at a temperaturefavorable for the reactionsv to occur, optimum cracking and reformingresults can be obtained and the products thus made can be preserved fromfurther decomposition or pyrolysis by quickly and immediately coolingthem through contact with a cooled surface, in equipment substantiallyas shown in the figures.

Even carbon black of good quality-can be obtained in this manner whenthe contact time is relatively long, in some cases 0.6 to severalseconds, the catalyst pieces have an average diameter of about A to inchor more and the maximum temperature in the catalyst mass is higher thanabout 700 C. Iron and nickel catalyze this reaction. In making carbon inthis manner it is quite essential that the pieces of catalyst comprisingmass 4 be of fairly uniform size and that the table I6 be rotated rathercontinuously during the cracking operation so that the maximum amount ofthe carbon formed is carried out entrained in the fluid stream. Thegeneral pro- 12 cedure is substantially as described above but it isquite advantageous to recirculate some of the products of reaction withthe hydrocarbon used for carbon production, and for the purpose of thisexample it will be considered that the air, hydrocarbon and whateversteam is used enter through valves llA, Iii-A and l8--A respectively andthat recirculated gas enters through valve 50. Although methane, ethaneand even higher molecular weight hydrocarbons when sufficiently dilutedare satisfactory for making carbon black, it is possible to make extraquality carbon black in this manner using unsaturated hydrocarbons suchas ethylene and propylene as basic raw material. I

Because of the importance of the method of making carbon black fromcarbon monoxide using my invention I desire to show by examplespecifically how this is accomplished, as follows:

Example VI.Referring to Figure 1, employing as a reactant, carbonmonoxide, and making carbon by the catalyzed reaction shown in Equation17:

The heat generated in this reaction is about 90,000 B. t. u. per 1000cubic feet of carbon monoxide. A mixture of about 20 per cent orsomewhat more of carbon monoxide with inert aeriform fluid is ideal forconducting the reaction without giving consideration to dissipation ofheat of reaction; the carbon and gaseous products carry away as sensibleheat substantially all of the heat generated in this case. The inertfluid preferably is nitrogen, steam, or mixtures, or stack gas which ispreferably substantially free from oxygen. Carbon black is formed inthis reaction at considerably lower temperatures than those at whichcarbon combines with carbon dioxide byreverse reaction to form carbonmonoxide and lower than those favorable for the water gas reaction tooccur. 400 C. is desired to initiate the reaction, it can economicallybe conducted at higher temperatures, limited by equilibrium relationsand reaction velocity. At temperatures above 450 C. the amount of carbonmonoxide in equilibrium with carbon and carbon dioxide'increases rapidlywith increments in temperature. The preferred temperature for initiatingthis reaction is below about 450 C. and the velocity of the reactantstream containing carbon monoxide through the catalyst mass issufficiently high so that secondary reactions between steam or' carbondioxide with hot carbon do not occur in appreciable amounts. Iron, orpartly carbidized iron, or chromium, is a suitable catalyst for thereaction. The iron, as borings or other form, is charged in the hopper 2and chamber l until they are filled. Then the iron in the reaction zoneis heated to about 450 C. by admitting burning gases into the iron mass;the combustible gas entering 20 through valve I9 is carbon monoxidereactant gas but couldbe any'combustible gas, and the air for itscombustion is admitted through valve l1. After the iron adjacent theinner baflles 6 is heated the air valve 1 I is closed but the stream ofmonoxide-laden gas is continued, the products of reaction passing outof'the iron mass as indicated by the arrows adjacent the cooling surface9 and then through ofitake 40 and 4| to suitable carbon removingequipment such as a Cottrell precipitator, which is t not a part of thisinvention. The heat of reaction Although a temperature of about 200 towhen the cleaning step is discontinued and the monoxide gas stream isagain started. Table I6 is preferably slowly rotated during the courseof production of the carbon; black. Air used for cleaning may beintroduced through 4'! and 42 during regular operation if desired but itdoes not clean the catalyst in the upper reaction zone. The dischargedcatalyst is used again or discarded according to its condition, value,and number of days used. Crushed iron ore, the oxides, carbonate, orhydroxyoxides, upon partial reduction, are satisfactory catalysts, hencethe spent catalyst can economically be discarded and used as feed stockfor a blast furnace, thus eliminating the necessity of cleaning ironcarbide catalyst.

The properties of the carbons made as described vary according to,duration of time that the reactant stream is in contact with thecatalyst mass, temperature attained in said mass by said stream, initialconcentration of the monoxide in the reactant stream, diluent employedwith the reactant, initial moisture content of the reactant stream, andother variables besides the nature and size of catalyst particles andrate of catalyst mass downwardly through the reaction chamber.

One excellent grade of carbon is made using crushed dense iron orecatalyst, pieces about /2 inch average diameter, with maximumtemperature of catalyst bed about 450 C. and mean thickness of bed inreaction zone about iii-inches.

Other reactions that are advantageously'conducted in the apparatus shownin Figure 1 are:

(A) Purification of gases containing hydrogen sulphide, employingiron-oxide as catalyst whereby the sulphide of iron forms and sulphur isalso formed, revivification taking place by the use of oxygen or air insitu or in another similar apparatus. The bed of iron catalyst is keptloosely packed by virtue of the rotation of table It. This procedure isapplicable to city-gas plants; reactions are promoted atlow'temperatures, commonly below 110 C.

(B) Olefins are preparedby dehydration of alcohols, as typified byEquation 18:

(1s) C2H5OH CzH4+H2O (favored by reduced.

pressure) using an active alumina catalyst at temperatures approximating320 C., at atmospheric pressure; the heated vapors of alcohol are simplypassed through the catalyst bed; Other dehydration reactions can equallywell be carried out in the same 4 manner and a large portion of thesensible heat of the products recovered; inert dilution of reac--peratures, or the preferential combustion of the sulphur compounds tosulphurdioxide can be accomplished by controlling the amount of oxidantused and the temperature of the catalyst mass. With proper adjustment ofair and gas the, sulphur compounds are converted to hydrogen sulphideand sulphur dioxide which react further to form sulphur at lowertemperatures, recoveris high enough to preventv able as such. Thus whena gas stream contain-' ing an appreciable amount of hydrogen sulphide ismixed with a predetermined amount of an oxygen-laden'gas and passedthrough a bedof refractory material in the manner already described,liquid sulphur can -be condensed from the efiiuent gas or sulphurdioxide produced according to Equations 19 and 20.

. namely below about 1050-C. and above about (D) Reforming ofhydrocarbon compounds by the cyclic steps, heating a bed of refractorysolids which may be catalyst, to incandescence by buming hydrocarbonvapors or gas with air in direct contact with said solids, by openingvalves 18 and I1, for a period, taking the products of com- ,bustionofi'through 40, then discontinuing the heating operation and passinghydrocarbon and steam, preferably superheated steam, through said bed byopening valves l9-A and l8-A, re-

, moving the stream of reactants through but keeping them. separate fromthe said products of combustion; some air or oxygen is introduced asoccasion warrants for the purpose of increasing the relative duration ofthe make" period and also for providing nitrogen-'in the finishedproduct when the re-formed gas is used for making ammonia or othernitrogen compound.

'The reactions are typified in Equations 21 to 24 inclusive.

,Heating reaction CH4+2O2=CO2+2H2O (22) Gas making reactionCH4+HzO=CO+3Ha 2Gas making reaction CH4+2H2O=CO2+4H2 4) Gas makingreaction For generating hydrogen for ammonia production I find that anyof the gaseous or vaporizable hydrocarbons, particularly paramnichydrocarbons, can be reformed in this manner and that it is possible toadjust the nitrogen content of the reformed product so that the Hz to Naratio will be 3 to 1, more than 3 to 1, or less than 3 to 1, as

desired, by adjusting the amount of air. used with the steam hydrocarbonmixture; increasing the proportion of air decreases this ratio and viceversa. Natural gas, natural gasolines or fractions thereof aresatisfactory raw materials for thesereactions. In this example table I6is rotated sufliciently to keep the bed of solid refractory material 4from channeling; the steam and air keep it free from any carbonaccumulacontact iron at said temperature.

unimportant use for this-process in the petroleum industry. Attention iscalled to the result obtained by a slight modification of conditions forproducing the CO and H2 mixtures, as follows:

Example VIL-Crackz'ng-reforming hydrocarbons When petroleum-naphtha,butane, natural gasoline, mixtures of them or fractions of them having amolecular weight greater than 16 is 01' about 850 C.-and within thelimits 0.2 to-2.0.

seconds at 650 to 750 0., very little carbon monoxide is formed, thereactions occurring are chiefly cracking-reactions and the productsformed are unsaturated hydrocarbons including butadiene, isoprene,ethylene, propylene, butylene, aromatics including xylene and benzene,

and methane and hydrogen. The heat required by these reactions ismuch-less than that for-those shown in Equations 22 and 23. By heatingthe steam used to a temperature of more than 500 to 600 C. very littleadditional heat is required and this amount can readily be supplied bythe use of a relatively small amount of air with the gas-steam mixture.Some of the results cracking commercial butane are as follows:

Steam used mole per mole of charge.

Vapors usedcommercial butane.

Maximum temperature of catalyst- 450 C.

Time contact-0.8 sec.

Propylene formed, grams per 100 gms. of butane passed-22.0.

. Butane cracked-37.0 per cent of the charge.

Ratio, gms. of propylene formed to ene formed- 5.0.

Catalyst-copper metal.

Air used during cracking-none.

Highetr unsaturates including butadiene--1.3 per cen Operation cyclic,alternate heating and cracking periods.

Employing higher. temperature, 800 0., the amount of butane "cracked perpass is appreciably increased, being more than 90.0 per cent, the totalunsaturates are high and although the methane content of the gas made isappreciable the hydrogen content is not high and little if any carbonforms provided the catalyst employed is not iron, unless steam is alsoused, and provided-the reacting fluid does not Vanadium chrome steeldoes not catalyze carbon formation like iron or ordinary steel. Theethylene-propylene ratio is higher at this temperature; it is higher at0.4 second time of contact than at 0.2 second at the same temperature.At 850 C. maximum temperature of the catalyst mass using steam inadmixture with the vapor to be cracked, the results are as follows:

Time of contact-0.2 to 0.4 second.

Mole ratio steam to vap0r4.0 to about 5.0.

Pressure-substantially atmospheric.

Liquid or readily liquifiable products formed,

charging petroleum naphtha is 50 weight percent of the naphtha charged.The yield of gms. of ethyl- 1s C4Hx hydrocarbons is about 8.0 to 10.0 orthe naphtha charged.

When less superheated steam is used, about 0.5 to 20 moles per mole ofthe hydrocarbon vapor, and a small amount of air used with the mixedsteam-hydrocarbon vapor, enough to substantially maintain a maximumtemperature in the catalyst mass of approximately 850 C. the results aresomewhat different and very little if any carbon is formed. The totalgas production is slightly increased, the readily liquiflable prod netsare not materially changed and although the amount of propylene andethyleneis large somepercent What more 04H): is produced in the finishedliquid products, and more COrand C02 are formed. In making unsaturatedhydrocarbons largely from saturated hydrocarbon this is the preferredop- 1 eration of my process. Less than 10.0 percent of the heat ofcombustion of the vapor reacted is consumed by combustion formaintaining the temperature of thebatalyst; by preheating the naphthaand air used operation can be conducted with only 3.8.prcent fuelconsumption with--.substantially continuous operation. The latter resultwas obtained using slightly more than 2 moles of water vapor orsuperheated steam per mole of vaporized gasoline. The 3.8 percent fuelconsuinption is the heat unitsused for internal combustion as percent ofthe total heat of combustion of the hydrocarbon charged. The time ofcontact of reactants with the catalyst mass was 0.13 second.

One of the advantages of conducting this type of reaction, operating inthe apparatus shown in Figural, is that the inner bafiies 6 can readilybe made of refractory non-metallic materials and when they are made asshown in Figure 2, they fit togetherforming a refractory duct with-- in,through which hot fluids can pass without the damage which would occurif iro'n baffles were i used. In other words unusually high temperaturescan be used when desired in the apparatus shown in Figure 1. 3

At low rates of flow of straight butane vapor in the stream passingthrough the catalyst mass,

rates approximating'one second contact time, the ,unsaturates in theoutgoing stream are as follows:

- Degrees C. 7.90 percent total unsaturates 600 20.80 percent totalunsaturates 650 36.80 percent total unsaturates 700 37.60 percent totalunsaturates 750' 35.60 percent total unsaturates 7'75 27.60 percenttotal unsaturates 800 "25.00 percent total unsaturates 820' However, atccnstant temperature and increasing velocity of flow the followingresults were ob- At somewhat lower temperature, at velocities so thighthat all of the butane charged is not cracked, andwithout using steam,there is formed obtains within said mass;

25 pounds of propylene per 100 pounds of butane per pass; recovering theuncracked butane and of butane or equivalent gas is required in order tomake the operation self-sustaining as to temperature in the catalystmass. However, the production of maximum butadiene and other C4unsaturated hydrocarbons is favored by the use of more. steam, namely 2to 4 moles per mole of hydrocarbon charged, high velocity of flow ofreactant stream, approximating 0.1 to 0.2 second time of contact withthe catalyst mass, and a small amount of air in the reactant fluidstream being approximately 3 to 5 percent of that required to completelyburn the hydrocarbon used.

One specialized use for the process described above "is the removal ofcarbon monoxide from hot hydrogen or other gas, in which it is usuallynot necessary to do more than pass the hot gas as a stream through amass of iron catalyst, pref-- erably not the oxide of iron, at atemperature of about 300 to 350 C. as described above for the productionof carbon black, preferably under super-atmospheric pressure. Carbon andiron carbide form along with carbon dioxide as reaction products; thecarbon and carbon dioxide pass out entrained in the gas whereas thecarbide is removed with and as the catalyst.

Another special case, one in which ;triple valuable reactionsproductsare made from one reactant, preferably diluted with an inert, isindicated by Equation 25 (favored by chromic oxide catalyst) whichrepreproducts mentioned, in the presence of catalyst l.

. v 18 through ll-A. The purpose of introducing the oxidant is to bringthe ethylene to the temperature favorable for cracking into the reactionthe Before defining my claims, attention is called to a few factorsrelating to the apparatus shown in Figure l, which I consider important,novel features, namely:

(1') The path of'travelof fluid reactantsthrough contact mass 4 isradial, therefore, the

lineal velocity of a given volume of said fluid is ucts. Dilution of thereactant with nitrogen or other diluent. is favorable to the reactionwhich is also favored by a reduction in the pressure at which thereaction is conducted. In this case, a

particularly valuable'carbon black is formed and the acetylene andhydrogen have known value and are readily separable from one another byknown means. The heated ethylene is given the final temperature boost bythe introduction of air, or oxygen enriched air, for the combustion of aportion of it, thus the ethylene stream entering the contact mass 4 ofFigure 1 from 20 and l9A is diluted and mixed with air from i'l--A andpreferably also with inert gas from 50. The reaction is endothermic thusthe gas stream leaves the mass 4 Ma lowertemperature than the suddencooling of the reaction products by contact with surface 9 is an aid inpreventing further decomposition and preserving the'acetylene formed.The preferred temperature for initiating the reaction indicated byEquation 25 is above 700 C. The amount of oxidant added through i'l-A isapproximately 4 to 10 percent of that required for complete combustionof the ethylene, the exact amount varying with the concentration of theethylene in the mixture, the temperature of the diluent gases from usedin the mixture, and the temperature of the gas stream introduceddecreasing throughout its travel through said mass. With exothermicreactions or, combustion supported reactions the hot zone is nearer theinner; bailles and the cooler zone near the outer bailles, hence thefluid stream travels at a higher v rate of flow through the hotter zone.

(2) The rate of downward travel of the catalyst, by virtue of rotationof table It, is not necessarily uniform over the whole thickness of thecatalyst bed between the inner and outer bailles 6 and I; by providing asteeper downward flare to the inner bailles, as shown, and by providinga rather long baffle [2 as shown, but without baffle l2-A, the travel ofcatalyst adjacent the inner bailles 6 is greater than that adjacentouter bailles 1.. This condition i readily reversed by placing bafile I!in the opposite position, namely, support it so as to flare downwardlyand outwardly from fluid tube 20, as shownby l2--A, and by providingsteeper sloping outer baflles I and wider flaring bailles 0. Thus, it ispossible to flned within a boiler which boiler is itself a means ofeconomizing heat: the boiler may be considered to be a surfacecombustion boiler.

(4) The inner series of baflles I with adJoining sections having ports 8can readily be. made of refractory material capable of withstanding hightemperatures hence endothermic reactions such as the steam reforming ofhydrocarbons formin CO and H2 accompanied by combustion reactions,wherein-initial temperatures of 950 C. are

provided, can be conducted without damage to f the equipment shown inFigure 1.

(5) The reaction zone is broadly a zone wherein fluids are treated andcaused to react chemically, by virtue of contact with a bed of confinedsolids, and in which solids also may react by virtueof contact with aflowing stream. The time of contact of a stream passing through thecatalyst mass confined between the two series of baffles 8 and I may begreat or very short according to rate of supply of the stream containingreactant fluid, but the low limit is greater than that which isaccompanied by appreciable entrainment of catalyst in the stream passingaway from the catalyst mass. This limit is a function of the density ofthe catalyst and particle size. At very low lineal stream velocities theapparatus becomes a filtering medium and is usable for treatingandclarifying fluids; here the advantages of decreasing lineal streamvelocity through the contact mass is advanta eous.

(6) Outer Jacket ii, of Figure 1, is shown as confining a liquid but itcan equally well be a means of superheating a vapor, when conditionswarrant. v

(7) When the solids in the reaction zone are wetted with a wettingagent, the apparatus'of Figure 1 will function as a dust removal medium,it being necessary merely to so proportion the chamber that the linealvelocity of the dustladen fluid introduced into 4 from duct 20 through 8is suiflciently low. Fog can also be removed from gases in this manner;likewise moisture can be absorbed from a'gas stream by selection ofproper solid absorbent.

(8) With a given rate of flow of an aeriform stream through the annularcolumn of solids confined between baflles 8 and I of Figure which column.has, for example, a mean inside diameter of 1 foot and a thickness of 1foot, an increase of 50 percent in thickness, that is, an increase from12 inches to 18 inches, will about double the time of contact of saidstream with the solids, whereas the lineal velocity of the stream as itleavesthe catalyst mass is reduced by about 33 percent, no correctionsmade for temperaturevolume change. v

(9) Proces steam is generated, in conducting high-temperature reactions,at a rate proportional to the amount of such reaction promoted, when thejacket H is the steam generating unit of a steam boiler. V

(10) This invention is believed to be particularly adapted to promotesubstantially complete dissociation of certain materials which do not,

require appreciable amounts of, if any, heat. Without unduly extendingthe description, reference is here made to a few reactions which arefavored, by Equations 26 and 27.

In each of these equations the reactions will proceed continuously as aheated stream of either CH4 or C2H4 is passed, in the manner describedreaction sought is conducted in eachreactor .of the series.-

I have found that by raising or lowering table I6 of Figure 1 the rateof discharge of solids is controlled as well as by rotation, hence I donot confine my invention to a particular means of removing the catalyst.

therethrough in intimate contact with said solids,

thereby causing chemical reactions to occur among the said reactantswhile passing through said column with the formation of valuablereaction products, immediately cooling the stream containing thereaction products by contacting it with a cooled solid surface, removingit therefrom and recovering the said stream containing reaction productsseparate from said solids; the amount of air used being insufficient forthe complete combustion of said hydrocarbon, and

throughout the process passing. the solid par 1 I ticles of said masscontinuously downwardly with free-flowing tumbling motion over a zigzagcourse at a rate sufllcient to keep the bed per,

vious to the passage of the aeriform fluid therethrough and favorablefor the production of said valuable reaction products.

2. The process of treating materials and promoting chemical reactions atan elevated temperature partly by contacting a reactive fluid with hotsolid contact, material, comprising, first causing a mass of small-sizesolids adapted to withstand being heated, confined in a reactionchamber, to be so disposed in a loosely packed, porous bed in the formof an upright annular column that said column has a plurality ofsubstantially circular, spaced, declivous, free inner surfaces and aplurality of substantially circular spaced, declivous, free outer-wallsurfaces, then passing a fluid stream, containing a hydrocrabon in'thevapor phase and an oxidizing gas, initially at a temperature above 100G. into said bed from within through said inner-wall. surfaces,promoting chemical reactions in said bed at a temperature of the orderof 600 C. to 900 C. forming at least one valuable reaction product,immediately discharging the stream containing said reaction productfrom'said bed from said outer-wall surfaces and recovering said product,meanwhile maintaining the required high tem-' perature in said bed atleast partly by controlling the supply of said oxidizing gas, andthroughout the process passing the solid particles of said masscontinuously downwardly with a free-flowing tumbling motion over azigzag course at a rate sufiicient to keep the bed pervious to thepassage of the aeriform fiuid therethrough and favorable for theproduction of said valuable, reaction products. i

3. The process of treating materials and pro-.

moting chemical reactions in a closed reaction chamber by contacting areactant fluid with a loosely packed, confined mass of small-sizesolids,

" comprising, passing a stream of aeriform fluid initially comprising ahydrocarbon and at least one member of a group consisting of steam andan oxidizing gas in insuflicient quantity to complete combustionof thehydrocarbon, at a tem- The present application is a division of myperature below about 900 C. but above C. from within a confined,upright, substantially annular, loosely packed column of said solids,substantially radially outwardly therethrough in ,in-

timate contact with said solids, thereby causing chemical reactions tooccur in said stream while passing through said column with theformation of valuable reaction products, immediately cooling the streamcontaining .the reaction products by contacting it with a cooled solidsurface, removing it therefrom and recovering the said stream containingreaction products separate from said solids, and throughout the processpassing the solid particles of said mass continuously downwardly with afree-flowing tumbling motion over a zigzag course at a rate sufiicientto keep the bed pervious to the passage of the aeriform fluidtherethrough and favorable for the production of said valuable reactionproducts.

4. The process of treating materials and promoting chemical reactionsina closed reaction chamber by contacting a reactant fluid with a looselypacked confined mass of small-size solids,

comprising, passing a stream of aeriform fluid initially comprising anoxidizing gas and a hydrocarbon, at a temperature below about 900 C. but

above 100 C. from within a confined, upright, substantially annular,loosely packed column of said-solids, substantially radially outwardlytherethrough in intimate contact with said solids,

thereby causing chemical reactions to occur in '5 said stream ofaeriform fluid while passing through said column with the formation ofvaluable reaction products, immediately cooling the stream containingthe reaction products by contacting it with a cooled solid surface,removing it carbon, and throughout the process passing the solidparticles of said mass continuously downwardly with a free-flowingtumbling motion over a zigzag course at a rate sufllcient to keep thebed pervious to the passage ofthe aeriform fluid therethrough andfavorable for the production of said valuable reaction products.

5. A process as set forth in claim 3 wherein the aeriform stream ofreactant fluid comprises a hydrocarbon and superheatedsteam.

6. A process as set forth in claim 3 wherein the the chemical reactionsin the reactant fluid 40" stream. I

8. A process as set'forth in claim 3 wherein the reactant fluid containspetroleum fractions which are treated at high temperatures for a shortperiod of time to produce a reaction'product containing unsaturatedcompounds. 1

- 9. A process as set forth in-claim 3 wherein petroleum fractions inthe reactant stream are 22 cracked by exposure to the heated contactsolidsv for a period of from 0.1 to 4 seconds.

10. A process as set forth in claim 3 wherein cracking temperatures ofabove 700 C. are employed for the production of aromatic compounds frompetroleum fractions in the reactant stream. 11. A process as set forthin claim 3 wherein the reactant stream contains hydrocarbon vapors whichare cracked by contact with said solida to 12. A process asset forth inclaim 3 wherein the aeriform stream is in contact with the solids for aperiod of 0.1 to 4 seconds and at a temperature within the range of 600C. to 900 C.

- JOHN J. ALLINSON.

' file of this patent: I g

UNITED STATES PATENTS Number Name Date 1,732,381 Schmidt et a1 Oct. 22.1929 1,995,292 Clark Mar. 26, 1935 1,995,293 Clark Mar. 26, 19351,972,937 Jaeger Sept. 11, 1934 1,560,297 Meigs -1 Nov. 3, 19251,963,258 Brode- June 19, 1934 1,984,380 Odell Dec. 18, 1934 2,340,814Li Dov Feb. 1, 1944 2,078,951 Houdry -1 May 4, 1937 2,187,741 HoudryJan.;30, 1940 2,265,837 Harding Dec. 9, 1941 2,303,717 Arveson Dec. 1,1942 2,338,573 Creelman Jan. 4, 1944 2,362,621 Fahnestock Nov. 14, 19442,364,453 Layng et al Dec. 5, 1944 2,376,365 Lassiat f May 22, 1945FOREIGN PATENTS Number Country Date 643,747 France Sept. 8, 1922.

Germany Sept. 8. 1931

